U.S. patent number 4,336,360 [Application Number 06/117,789] was granted by the patent office on 1982-06-22 for process for the stereoregular polymerization of alpha-olefins.
This patent grant is currently assigned to Montecatini Edison S.p.A.. Invention is credited to Antonio Cassata, Umberto Giannini, Paolo Longi, Romano Mazzocchi.
United States Patent |
4,336,360 |
Giannini , et al. |
* June 22, 1982 |
Process for the stereoregular polymerization of alpha-olefins
Abstract
There is disclosed a process for the stereoregular
polymerization of alpha-olefins or mixtures thereof with ethylene,
conducted in the presence of highly active and stereospecific new
catalysts. The catalysts are obtained from the reaction of a
particular Al-alkyl compound which is at least in part in the form
of a complex and/or a substitution reaction product with an ester
of an oxygenated organic or inorganic acid, with a supported
component characterized by having surface area exceeding certain
values or showing a particular X-rays spectrum, and obtained by
contacting a Ti halogenated compound, preferably in the form of a
complex with an electron-donor compound, with a support comprising
a Mg or Mn bihalide in an activated condition. In the catalysts the
ratio between the Ti compound, expressed in Ti g-atoms, and the g
moles of the ester and the electron-donor compound, when present,
is lower than 0.3.
Inventors: |
Giannini; Umberto (Milan,
IT), Cassata; Antonio (Milan, IT), Longi;
Paolo (Milan, IT), Mazzocchi; Romano (Pernate,
IT) |
Assignee: |
Montecatini Edison S.p.A.
(Milan, IT)
|
[*] Notice: |
The portion of the term of this patent
subsequent to August 15, 1995 has been disclaimed. |
Family
ID: |
11219117 |
Appl.
No.: |
06/117,789 |
Filed: |
February 1, 1980 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
955762 |
Oct 30, 1978 |
4187196 |
|
|
|
795363 |
May 9, 1977 |
|
|
|
|
503766 |
Sep 6, 1974 |
|
|
|
|
265455 |
Jun 23, 1972 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Jun 25, 1971 [IT] |
|
|
26275 A/71 |
|
Current U.S.
Class: |
526/114; 526/128;
526/125.6; 526/124.6; 526/125.4; 526/124.4 |
Current CPC
Class: |
C08F
4/022 (20130101); C08F 10/00 (20130101); C08F
10/00 (20130101); C08F 4/6543 (20130101); C08F
10/00 (20130101); C08F 4/695 (20130101); C08F
10/00 (20130101); C08F 4/654 (20130101); C08F
10/00 (20130101); C08F 4/646 (20130101); C08F
10/00 (20130101); C08F 4/6428 (20130101); C08F
10/00 (20130101); C08F 4/6583 (20130101) |
Current International
Class: |
C08F
4/00 (20060101); C08F 10/00 (20060101); C08F
4/02 (20060101); C08F 004/02 (); C08F 010/00 () |
Field of
Search: |
;526/114,125 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
625748 |
|
Aug 1961 |
|
CA |
|
1958046 |
|
Jun 1970 |
|
DE |
|
2029992 |
|
Dec 1970 |
|
DE |
|
2153520 |
|
May 1972 |
|
DE |
|
918740 |
|
Feb 1963 |
|
GB |
|
1128724 |
|
Oct 1968 |
|
GB |
|
Primary Examiner: Smith; Edward J.
Parent Case Text
This is a continuation of application Ser. No. 955,762 filed Oct.
30, 1978 and now U.S. Pat. No. 4,187,196 which in turn is a
continuation of Ser. No. 795,363 filed May 9, 1977 and now
abandoned; which in turn is a continuation in part of Ser. No.
503,766 filed Sept. 6, 1974 and now abandoned; which in turn is a
continuation of Ser. No. 265,455 filed June 23, 1972 and now
abandoned.
Claims
We claim:
1. Process for the stereoregular polymerization of alpha-olefins of
the formula CH.sub.2 .dbd.CHR wherein R is an alkyl radical having
1-6 carbon atoms and mixtures thereof with ethylene, which process
comprises polymerizing the olefins in contact with a catalyst the
starting catalyst-forming components of which comprise:
(a) an addition reaction product of an electron-donor compound (or
Lewis base) selected from the group consisting of esters of silicic
acid with an Al-trialkyl compound or with an Al-alkyl compound
containing two or more Al atoms linked together through an oxygen
or a nitrogen atom, the amount of Al-alkyl compound contained in a
combined form with the ester in catalyst-forming component (a)
being from 0.05 to 1.0 mole per mole of the starting Al-compound;
and
(b) the product obtained by contacting a Ti compound selected from
the group consisting of halogenated bi-, tri-, and tetravalent Ti
compounds and complexes of said Ti compounds with an electron-donor
compound, with a support which comprises, as the essential support
material thereof, an anhydrous bihalide of Mg or Mn in an active
state such that the X-rays powder spectrum of component (b) does
not show the most intense diffraction lines as they appear in the
X-rays powder spectrum of normal, nonactivated Mg or Mn bihalide,
the X-rays powder spectrum of component (b) showing a broadening of
said most intense diffraction lines.
Description
THE PRIOR ART
Highly active supported catalysts suitable for the olefin
polymerization and obtained from metallorganic compounds of the
metals of the I, II and III Group of the Periodic System and Ti
compounds supported on Mg or Mn dihalides present in an active form
have been disclosed for instance in Belgian Pat. Nos. 742,003,
742,112 and 754,152.
These catalysts are highly active in the polymerization of
ethylene. When the catalysts are used for polymerizing alpha
olefins, in particular propylene, they produce predominantly
amorphous atactic polymers.
It is known that the activity and/or stereospecificity of Ziegler
and Ziegler-Natta catalysts can be modified by adding to the
catalysts certain Lewis bases. Generally the Lewis bases are used
in the form of complexes with the Ti compound. However, catalysts
are known in which the base can be used in an amount as high as to
reach a 1:1 molar ratio with the Al compound.
When the polymerization of propylene is carried out with supported
catalysts of the type described in the above mentioned Belgian
patents, wherein the Ti compound is used in the form of a complex
with a Lewis base, the stereospecificity of the catalyst is
increased but the amount of the amorphous polymer is still too
high. The thus modified supported catalysts do not find in practice
any application in the polymerization of alpha-olefins.
In the Ziegler and Ziegler-Natta catalysts the molar ratio Al:Ti
generally is not higher than 5-10:1. The preferred values range
from 3:1 to 1:1.
When the ratios become as high as the ratios used in the supported
catalysts wherein the amount of the Ti compound is very small in
comparison with the Al-alkyl compound, the addition to the
catalysts of a Lewis base has the effect of drastically lowering
the activity of the catalysts.
From the above outlined behavior of the Ziegler and Ziegler-Natta
catalysts modified with Lewis bases one would have expected that
the sole way for obtaining supported catalysts still active and
endowed with a certain stereospecificity was to use the Ti
compounds in the form of a complex with a Lewis base.
THE PRESENT INVENTION
One object of this invention is to provide a process for the
production with high yield of prevailingly isotactic polymers of
alpha-olefins CH.sub.2 .dbd.CHR, wherein R is an alkyl radical
containing from 1 to 6 carbon atoms.
A particular object of the invention is to provide a process for
the production with high yield of prevailingly isotactic polymers
of propylene.
A further object is to provide a process for the production of
prevailingly isotactic polymers of propylene having satisfactory
impact resistance at low temperatures and containing 1-20% by
weight of polymerized ethylene.
These and other objects are accomplished by the present invention
in accordance with which the polymerization of the alpha-olefins
and mixtures thereof with minor proportions of ethylene is
conducted in the presence of the new catalysts disclosed infra.
As peculiar characteristic these new catalysts associate very high
activity with a remarkable stereospecificity. Owing to this
characteristic and in particular to the fact that the activity of
the catalysts is not remarkably reduced by the presence of hydrogen
as molecular weight regulator during the polymerization process,
the new catalysts permit to avoid or at least to considerably
simplify the onerous treatments hitherto necessary for purifying
the polymers from the catalyst residues.
The catalysts used in the process of this invention are the product
of the reaction between:
(a) the addition and/or substitution reaction product of an
electron donor compound (or Lewis base) selected from the group of
the esters of the oxygenated organic and inorganic acids with an
Al-trialkyl compound or with an Al-alkyl compound containing two or
more Al atoms linked together through an oxygen or a nitrogen atom,
the reaction product (a) being characterized in that the Al-organic
compound present in combined form with the ester is comprised
within the range from 0.05 to 1 mole per mole of the starting
Al-compound.
(b) the product formed from the contact of a halogenated compound
of bi, tri or tetravalent Ti, preferably in the form of an addition
compound with an electron-donor compound, with a support formed of
or comprising an anhydrous bihalide of Mg or Mn, the support and
the component (b) being characterized in that they have surface
area exceediing 3 m.sup.2 /g or the component (b) being
characterized in that in its X-rays powder spectrum the most
intense diffraction lines characteristic of the X-rays powder
spectrum of the normal, non activated Mg and Mn bihalides, are
broadened and the component (b) being further characterized in that
the amount of the Ti-compound therein present, expressed as Ti
metal, is less than 0.3 g atom per mole of the total amount of the
electron-donor compound present in a combined form in the
catalyst.
By the expression "addition or substitution reaction product" of
the electron-donor compound indicated sub (a) with the Al-alkyl
compound is intended the product formed of or comprising a complex
of the electron-donor compound with the Al-alkyl compound.
Any electron-donor compound of the class of the esters of the
oxygenated organic and inorganic acids is suitable to prepare the
component (a) of the catalysts.
Examples of esters which can be used are: esters of aliphatic,
cycloaliphatic and aromatic mono and polycarboxylic acids; esters
of alkoxy or amino acids; esters of inorganic acids like carbonic,
phosphorous, sulphuric, phosphoric and silicic acids.
Examples of specific compounds are: ethylbenzoate, methylbenzoate,
ethyl-p-methoxybenzoate, ethyl-p-butylbenzoate,
ethyl-p-chlorobenzoate, ethyl-p-butoxybenzoate, isobutylbenzoate,
ethyl-p-methylbenzoate, ethylacetate ethyl propionate,
ethylalpha-naphthoate, ethylcyclohexanoate, ethyl pivalate, ethyl
N,N-diethyl-carbamate, diethyl carbonate, diethylsulphate,
dimethylmaleate, ethyl-benzensulfonate.
The most interesting results both with respect to activity and
stereospecificity of the catalyst, are obtained with the esters of
the aromatic acids like: ethylbenzoate, ethyl-p-methoxybenzoate;
ethyl alpha naphthoate. The preferred molar ratio ester/Al organic
compound in component (a) is lower than 1; in general it ranges
from 0.3 to 0.5.
The following Al-trialkyl compounds are particularly suited for
preparing component (a): Al(C.sub.2 H.sub.5).sub.3 ;
Al(CH.sub.3).sub.3 ; Al(nC.sub.3 H.sub.7).sub.3 and Al(iC.sub.4
H.sub.9).sub.3.
Examples of other Al-trialkyls are: ##STR1##
The metallorganic compounds which contain two or more Al atoms
linked through an O or N atom are obtained by reaction of an
Al-trialkyl compound with water, ammonia or a primary amine,
according to known methods.
Examples of such compounds are: (C.sub.2 H.sub.5).sub.2
Al-O-Al(C.sub.2 H.sub.5).sub.2 and ##STR2##
The component (a) of the catalyst can be obtained by several
methods. The preferred method consists in prereacting the ester
with the Al-organic compound in the adequate molar ratio before
contact thereof with component (b).
The starting molar ratio ester/Al-organic compound varies in
general from 0.95 to 1.
Another adequate method for preparing component (a), which at the
same time permits to obtain the Mg and Mn halide in an active form
suitable for preparing the catalysts according to this invention,
consists in reacting an addition compound between the Mg or
Mn-halide and an ester of an oxygenated organic or inorganic acid
with an Al-trialkyl employed in such a quantity that the
Al-trialkyl/ester molar ratio is higher than 1.
According to another method, component (a) is formed in situ by
reacting the Al-trialkyl compound with the component (b) and then
adding the ester in the quantity suitable for forming component
(a).
The electron donor compounds which can be employed in preparing
component (b) can be the same esters as those used in preparing
component (a) or can be different. Also, in this case any
electron-donor compound capable of giving complexes with the
halogenated Ti compound is suitable for preparing component
(b).
Examples of electron-donor compounds are:
N,N,N',N'-tetramethylethylenediamine veratrol, ethyl benzoate,
acetone, 2,5-hexanedione, dimethylmaleate, dimethylmalonate,
tetrahydrofurfurylmethylether, nitrobenzene, diethyl carbonate,
acetophenone, 1,2,4-trimethyl piperazine, ethyl acetate.
The diamines and the esters of oxygenated organic and inorganic
acids are particularly suitable both with respect to the activity
and stereospecificity of the catalyst.
The Ti compounds which can be employed include any halogenated
compounds of bi, tri and tetravalent Ti. Examples of such compounds
are: TiCl.sub.4, TiCl.sub.3, TiI.sub.4, Ti(OC.sub.3
H.sub.7)Cl.sub.3, Ti(OC.sub.4 H.sub.9).sub.2 Cl.sub.2,
3TiCl.sub.3.AlCl.sub.3, Ti[O-C(CH.sub.3).dbd.CH-CO-CH.sub.3 ].sub.2
Cl.sub.2, Ti[N(C.sub.2 H.sub.5).sub.2 ]Cl.sub.3, Ti[N(C.sub.6
H.sub.5).sub.2 ]Cl.sub.3, Ti(C.sub.6 H.sub.5 COO)Cl.sub.3,
[N(C.sub.4 H.sub.9).sub.4 ].sub.2 TiCl.sub.6, [N(CH.sub.3).sub.4
]Ti.sub.2 Cl.sub.9, TiBr.sub.4, TiCl.sub.3 OSO.sub.2 C.sub.6
H.sub.5, LiTi(OC.sub.3 H.sub.7).sub.2 Cl.sub.3.
The catalyst component (b) may also be prepared according to
various methods. One method consists in contacting the Mg or Mn
halide, which can be present in a preactivated form, with the Ti
compound previously complexed with the base and carrying out the
contact under conditions at which the resulting product has a
surface area higher than 3 m.sup.2 /g and/or its X-rays spectrum
shows a broadening of the most intense diffraction lines
characteristic of the normal non-activated Mg and Mn bihalides.
This can be obtained, e.g., by dry milling the support in the
presence of the Ti compound.
Good results are also obtained by simply mixing the Ti compound
with preactivated Mg or Mn bihalides having surface area exceeding
3 m.sup.2 /g.
Another method, according to which the complex of the Ti compound
with an ester is formed in situ, consists in adding the ester
suitable to form component (a) either before or after the addition
of the Al-alkyl to the previously supported Ti compound.
Examples of useful Ti addition compounds are: TiCl.sub.4.C.sub.6
H.sub.5 COOC.sub.2 H.sub.5 ; TiCl.sub.4.2C.sub.6 H.sub.5 COOC.sub.2
H.sub.5 ; TiCl.sub.4.pCH.sub.3 OC.sub.6 H.sub.4 COOC.sub.2 H.sub.5
; TiCl.sub.4.C.sub.6 H.sub.5 NO.sub.2 ; TiCl.sub.3.(CH.sub.3).sub.2
N(CH.sub.2).sub.2 N(CH.sub.3).sub.2 ; TiCl.sub.4, (CH.sub.3).sub.2
N(CH.sub.2).sub.2 N(CH.sub.3).sub.2 ; TiCl.sub.4.CH.sub.3 COC.sub.2
H.sub.5 ; TiCl.sub.4.2C.sub.4 H.sub.8 O; TiCl.sub.3.C.sub.6 H.sub.5
COOC.sub.2 H.sub.5.
The quantity of Ti compound present on the support is generally
comprised between 0.1 and 10% by weight expressed as Ti metal. The
quantity of Ti compound present in the catalyst expressed as Ti
metal is less than 0.3 g-atom per mole of the total amount of
electron donor-compound present in combined form in the catalyst;
preferably said quantity is less than 0.1 g-atoms and more
particularly it is comprised between 0.05 and 0.005 g-atoms. The
Al/Ti molar ratio is generally comprised between 10 and 1000.
The expression Mg and Mn bihalide in active form as used herein
refers to Mg and Mn bihalides having surface area exceeding 3
m.sup.2 /g and/or said bihalides the X-rays powder spectrum of
which shows a broadening of the most intense diffraction lines
characteristic of the normal non-activated Mg and Mn bihalides.
The Mg and Mn bihalides in the active form may be prepared
according to various methods.
In the particular embodiment of our invention with which this
application is concerned, normal anhydrous Mg or Mn bihalide is
converted to the active form by reacting it with an electron-donor
which is an ester of an oxygenated organic or inorganic acid
followed by decomposition of the resulting reaction product or
complex by treatment thereof with an Al tri-alkyl used in an amount
such that the Al trialkyl/ester molar ratio is higher than 1.
Anhydrous compounds of elements of the Ist, IInd, IIrd and IVth
group of the periodic system different from the Mg and Mn bihalides
may be added to the activated Mg or Mn halides without
substantially reducing the activity of the catalyst obtainable
therefrom, but with the advantage of diminishing or even annulling
the negative effects of the high chloride contents in the
polymer.
In order to avoid any substantial alteration in the catalyst
activity, the anhydrous compounds of the Ist, IInd, IIIrd and IVth
group different from the Mg and Mn bihalides must not substantially
interact with the Mg or Mn halides.
Typical examples of the compounds of Group I to IV metals useful as
diluents of the activated Mg or Mn bihalide support are: LiCl,
CaCO.sub.3, CaCl.sub.2, SrCl.sub.2, BaCl.sub.2, Na.sub.2 SO.sub.4,
Na.sub.2 CO.sub.3, TiO.sub.2, Na.sub.2 B.sub.4 O.sub.7, Ca.sub.3
(PO.sub.4).sub.2, CaSO.sub.4, BaCO.sub.3, Al.sub.2
(SO.sub.4).sub.3, B.sub.2 O.sub.3, SiO.sub.2, etc.
The quantity of these substances which can be incorporated with the
Mg and Mn anhydrous halide, without substantially altering the
activity of the catalyst obtained therefrom, may vary in a broad
interval which may e.g., range from 30 to 70% by weight. As already
indicated, the surface area of the support consisting of or
comprising the activated anhydrous bihalide of Mg and Mn is larger
than 3 m.sup.2 /g. Good results have been obtained with surface
areas ranging from 20 to 30 m.sup.2 /g.
It has been found, and this constitutes another aspect of the
process of this invention, that the polymerization of propylene can
be carried out in liquid phase in the substantial absence of inert
diluents without appreciably reducing the isotacticity index of the
obtained polymer. This result is unexpected and surprising since
operating with catalysts supported on MgCl.sub.2 in which only the
Ti compound is used in form of a complex the stereospecificity of
the catalyst is remarkably reduced when the polymerization is
conducted in liquid propylene.
The use of liquid propylene permits on the other hand with respect
to the process carried out in presence of an inert diluent to
considerably increase the polymerization rate, with a resulting
higher hourly output of the polymerization reactors.
The conditions under which the polymerization of the alpha-olefins
with the aid of these new catalysts is conducted are those known in
the art. Thus, the polymerization is carried out at temperatures
ranging from -80.degree. C. to 150.degree. C., preferably from
40.degree. C. to 100.degree. C., operating with partial pressures
of the alpha-olefins higher than the atmospheric pressure. The
polymerization can be carried out both in liquid phase in the
presence of, or in the absence of, an inert liquid diluent, or in
the gas phase.
The alpha-olefins comprise, in general, olefins CH.sub.2 .dbd.CHR
in which R is an alkyl radical containing 1-6 C. propylene,
butene-1, 4-methylpentene-1 are examples of alpha-olefins. As
herebefore indicated the process can be used to polymerize mixtures
of alpha-olefins with minor proportions of ethylene.
Examples of inert diluents which can be used in the polymerization
are the C.sub.4 -C.sub.8 aliphatic hydrocarbons typical of which
are n-hexane, n-heptane, the cycloaliphatic hydrocarbons like
cyclohexane and the aromatic hydrocarbons such as benzene, toluene,
xylene.
The production of prevailingly isotactic polypropylene having
satisfactory impact resistance at low temperatures and containing
from 1 to 20% by weight of polymerized ethylene is also carried out
under conventional conditions, in accordance with which propylene
is either polymerized in the presence of small amounts of ethylene
fed continuously or intermittently into the reactor or ethylene is
polymerized after at least 80% of the propylene is converted to
polypropylene.
The regulation of the molecular weight of the polymer during the
polymerization is also carried out according to known methods,
operating, e.g., in the presence of alkyl halides, Zn or Cd
organo-metallic compounds, or hydrogen. As already mentioned the
presence of hydrogen as molecular weight regulator in the process
according to this invention does not appreciably reduce the
activity and/or stereospecificity of the catalysts.
The invention is described in more detail in the following examples
which are given only as illustrative and not intended to be
limiting. Unless otherwise specified, the percentages mentioned in
the examples are expressed by weight; the inherent viscosity of the
polymer .eta..sub.in was measured in tetralin at 135.degree. C.,
using concentrations of 0.25 g polymer in 100 cm.sub.3 solvent.
EXAMPLE 1
11.777 g anhydrous MgCl.sub.2 and 0.7924 g of the complex
TiCl.sub.4.(CH.sub.3).sub.2 N--CH.sub.2 CH.sub.2
--N(CH.sub.3).sub.2 are milled in a nitrogen atmosphere for 16
hours in a glass mill (length 100 mm, diameter 50 mm) containing
550 g steel balls having a diameter of 9.5 mm. The surface area of
the milled product was 8 m.sup.2 /g. 0.7697 g of the thus milled
mixture (having a Ti content of 0.993 by weight) are suspended in
the solution (previously prepared at room temperature and
maintained at this temperature for 10') of 0.82 g Al(C.sub.2
H.sub.5).sub.3 and 0.316 g ethyl benzoate in 50 cm.sup.3 anhydrous
and deareated n-heptane, and the thus obtained suspension is
injected under pressure of dry argon, into a stainless steel
autoclave having a 3 l capacity, provided with magnetic stirring,
heated to the temperature of 65.degree. C. and containing 900 g
anhydrous propylene. Stirring is discontinued after 6 hours, the
unpolymerized propylene is discharged and a white, pulverulent
product is removed from the autoclave which, after drying, amounts
to 228 g corresponding to a yield of 30,000 g polymer per gram of
titanium employed. The extraction with boiling n-heptane gave a
residue of 93.5%.
The inherent viscosity of the crude polymer is =5.08 dl/g.
EXAMPLE 2
8.86 g anhydrous MgCl.sub.2 and 0.699 g of the complex
TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are milled under a
nitrogen atmosphere for 16 hours in a glass mill, as described in
example 1. The surface area of the milled product was 32 m.sup.2
/g. The X-rays spectrum of the product showed a broadening of the
most intense diffraction lines characteristic of MgCl.sub.2.
0.1507 g of the thus obtained mixture (having a Ti content of 1.03%
by weight) are suspended in the solution (previously prepared at
room temperature and maintained at this temperature for 5') of
0.655 g Al(C.sub.2 H.sub.5).sub.3 and 0.252 g ethyl benzoate in 50
cm.sup.3 anhydrous n-heptane and the thus obtained suspension is
injected under pressure of dry argon, into a stainless steel
autoclave having a 2 l capacity provided with magnetic stirring,
heated to a temperature of 65.degree. C. and containing 500 g
anhydrous propylene.
After 6 h, stirring is discontinued, the unpolymerized propylene is
discharged and a white pulverulent product is removed from the
autoclave which, after drying, amounts to 112 g, corresponding to a
yield of 72,300 g polymer per g of Ti employed.
The extraction with boiling n-heptane gave a residue of 92.2%. The
inherent viscosity of the crude polymer is=3.68 dl/g.
EXAMPLE 3
9.51 g anhydrous MgCl.sub.2 and 0.74 g of the 1:1 molar complex
between TiCl.sub.4 and veratrol are milled in a nitrogen atmosphere
for 16 hours in a glass mill as described in example 1.
Using 124.7 mg of the thus prepared mixture and polymerizing
propylene under the conditions described in example 2, 70 g
polypropylene are obtained which correspond to a yield of 53,000 g
polymer per gram of titanium employed.
The extraction with boiling n-heptane gave a residue of 74%.
The inherent viscosity of the crude polymer is=4.42 dl/g.
EXAMPLE 4
10.1 g anhydrous MgCl.sub.2 and 0.62 g of the 1:1 molar complex
between TiCl.sub.4 and tetrahydrofurfuryl methylether are milled
under a nitrogen atmosphere for 16 hours in a glass mill as
described in example 1.
Using 196.5 mg of the thus prepared mixture and polymerizing
propylene under the conditions described in example 2, 70 g polymer
are obtained which correspond to a yield of 37,600 g polymer per
gram of titanium employed. The extraction with boiling n-heptane
gave a residue of 77.3%. The inherent viscosity of the crude
polymer is 4.9 dl/g.
EXAMPLE 5
9.62 g anhydrous MgCl.sub.2 and 0.65 g of the complex
TiCl.sub.4.CH.sub.3 --CO--CH.sub.2 --CH.sub.2 --CO--CH.sub.3 are
milled under a nitrogen atmosphere for 16 hours in a glass mill as
described in example 1.
Using 135.3 mg of the thus prepared mixture and polymerizing
propylene under the conditions described in example 2, 33 g polymer
are obtained which correspond to a yield of 24,400 g/g Ti. The
extraction with boiling n-heptane gave a residue of 84.7%. The
inherent viscosity of the crude polymer was 3.82 dl/g.
EXAMPLE 6
9.33 g anhydrous MgCl.sub.2 and 0.65 g of the complex
TiCl.sub.4.2CH.sub.3 --CO--CH.sub.3 are milled under a nitrogen
atmosphere in a glass mill as described in example 1.
Using 169 mg of the thus prepared mixture and polymerizing
propylene under the conditions described in example 2, 88 g polymer
are obtained which correspond to a yield of 51,000 g/g Ti. The
extraction with boiling n-heptane gave a residue of 86.3%. The
inherent viscosity of the crude polymer is=3.7 dl/g.
EXAMPLE 7
8.95 g anhydrous MgCl.sub.2 and 0.67 g of the 1:1 in moles complex
between TiCl.sub.4 and dimethyl maleate are milled under a nitrogen
atmosphere for 16 hours in a glass mill as described in example 1.
Using 147.4 mg of the thus obtained mixture and polymerizing
propylene under the conditions of example 2, 34 g polymer are
obtained which correspond to a yield of 23,000 g/g Ti.
The extraction with boiling n-heptane gave a residue of 85.2%. The
inherent viscosity of the crude polymer is 4.18 dl/g.
EXAMPLE 8
9.59 g anhydrous MgCl.sub.2 and 0.67 g of the 1:1 in moles complex
between TiCl.sub.4 and nitrobenzene are milled under a nitrogen
atmosphere in a glass mill as described in example 1.
Using 196.8 mg of the thus prepared mixture and polymerizing
propylene under the conditions described in example 2, 64 g polymer
are obtained after 5 hours, which correspond to a yield of 32,500
g/g Ti.
The extraction with boiling n-heptane gave a residue of 85.4%. The
inherent viscosity of the crude polymer is 3.72 dl/g.
EXAMPLE 9
10.66 g anhydrous MgCl.sub.2 and 0.69 g of the 1:1 in moles complex
between TiCl.sub.4 and diethyl carbonate were milled under a
nitrogen atmosphere, for 16 hours, in a glass mill as described in
example 1.
Using 164.6 mg of the thus prepared mixture, and polymerizing
propylene under the conditions described in example 2 after 5
hours, 222 g of polymer are obtained which correspond to a yield of
142,000 g/g Ti.
The extraction with boiling n-heptane gave a residue of 82.6%. The
inherent viscosity of the crude polymer is 3.54 dl/g.
EXAMPLE 10
10.57 g anhydrous MgCl.sub.2 and 0.45 g TiCl.sub.4 are milled
together under the conditions described in example 1.
131.4 mg of the thus obtained mixture are suspended in 50 cm.sup.3
n-heptane and in the thus obtained suspension there are added
successively 0.655 g Al(C.sub.2 H.sub.5).sub.3 and 0.252 g ethyl
benzoate.
After 5 minutes the thus prepared heptane suspension is injected
under pressure of dry argon into a stainless steel autoclave having
a 2 l capacity, heated to a temperature of 65.degree. C. and
containing 500 g anhydrous propylene. After 6 hours, stirring is
discontinued and 80 g polymer are separated from the mixture, in
the way described in example 2, which correspond to a yield of
59,300 g/g Ti.
The extraction with boiling n-heptane gave a residue of 82.1%.
The inherent viscosity of the crude polymer is 3.72 dl/g.
EXAMPLE 11
Example 10 was repeated using 160.9 mg of the product obtained by
milling together MgCl.sub.2 and TiCl.sub.4 and inverting the order
of addition of aluminium triethyl and ethyl benzoate.
74 g of polymer are thus obtained, which correspond to a yield of
44,600 g/g Ti. The extraction with boiling n-heptane gave a residue
of 83%.
The inherent viscosity of the crude polymer is 3.32 dl/g.
EXAMPLE 12
4.99 g anhydrous MgBr.sub.2 and 0.40 g of the complex
TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are milled together
under the conditions described in example 1.
Using 144 mg of the thus obtained mixture and polymerizing
propylene under the conditions described in example 2 after 5 hours
polymerization 178 g polymer are obtained which correspond to a
yield of 118,000 g/g Ti.
The extraction with boiling n-heptane gave a residue of 82%. The
inherent viscosity of the crude polymer is 2.88 dl/g.
EXAMPLE 13
30 g anhydrous MnCl.sub.2 are dissolved in 100 cm.sup.3 anhydrous
ethanol.
A powder having a specific area of 22 m.sup.2 /g is obtained by
fast evaporation of the alcohol and subsequent drying at
300.degree. C., under reduced pressure of 0.1 mm Hg.
7.96 g of the thus obtained product and 0.685 g of the complex
TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are milled together
for 40 hours, under the conditions described in example 1.
Using 170.3 mg of the thus prepared product and polymerizing
propylene under the conditions described in example 2, after 5
hours polymerization, 64 g polymer are obtained which correspond to
a yield of 33,500 g/g Ti. The extraction with boiling n-heptane
gave a residue of 74.3%.
The inherent viscosity of the crude polymer is 2.5 dl/g.
EXAMPLE 14
8.47 g anhydrous MgCl.sub.2 and 1.37 g ethyl benzoate are milled as
described in example 1 for 16 hours. After said period of time,
1.188 g of the complex TiCl.sub.4.2C.sub.6 H.sub.5 COOC.sub.2
H.sub.5 is introduced into the mill and is milled for another 16
hours.
The X-rays spectrum of the milled product shows a broadening of the
most intense diffraction lines characteristic of the X-rays
spectrum of MgCl.sub.2.
0.4116 g of the thus obtained mixture (having a Ti content of 1.05%
by weight) are suspended in the solution of 0.82 g Al(C.sub.2
H.sub.5).sub.3 and 0.241 g C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 in 50
cm.sup.3 anhydrous n-heptane.
The thus obtained suspension is injected under pressure of dry
argon into a stainless steel autoclave, having a 3 l capacity
provided with magnetic stirring, heated to the temperature of
65.degree. C. and containing 900 g anhydrous propylene.
After 5 hours polymerization, 315 g polymer are obtained which
correspond to a yield of 73,000 g/g Ti.
The extraction with boiling n-heptane gave a residue of 85.5%. The
inherent viscosity of the crude polymer is=3.7 dl/g.
EXAMPLE 15
4.2 g anhydrous MgCl.sub.2, 3.23 g anhydrous Na.sub.2 CO.sub.3 and
0.63 g of the complex TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5
are milled together under a nitrogen atmosphere, for 40 hours,
under the conditions described in example 1. The X-rays spectrum of
the milled product shows a broadening of the most intense
diffraction lines of MgCl.sub.2.
Using 172.9 mg of the thus prepared mixture (having a Ti content of
1.1% by weight) and polymerizing propylene under the conditions
described in example 2 after 5 hours, 232 g polymer are obtained,
which correspond to a yield of 122,000 g/g Ti.
The extraction with boiling n-heptane gave a residue of 87.4%. The
inherent viscosity of the crude polymer is=3.86 dl/g.
EXAMPLE 16
8.75 g anhydrous MgCl.sub.2 and 0.76 g of the 1:1 molar complex
between TiCl.sub.4 and dimethyl phthalate were milled together
under a nitrogen atmosphere for 16 hours in a glass mill as
described in example 1.
Using 155.8 mg of the thus prepared mixture and polymerizing
propylene under the conditions described in example 2 after 5
hours, 58 g polymer are obtained which correspond to a yield of
37,100 g/g Ti. The extraction with boiling n-heptane gave a residue
of 87.5%. The inherent viscosity of the crude polymer is 3.5
dl/g.
EXAMPLE 17
9.35 g anhydrous MgCl.sub.2 and 0.67 g of the complex
TiCl.sub.4.CH.sub.3 COOC.sub.2 H.sub.5 were milled together as
described in example 1. Using 139.2 mg of the thus prepared mixture
and polymerizing propylene under the conditions described in
example 2 after 5 hours reaction, 154 g polymer are obtained which
correspond to a yield of 96,800 g/g Ti. The extraction with boiling
n-heptane gave a residue of 85.5%.
The inherent viscosity of the crude polymer is 3.94 dl/g.
EXAMPLE 18
10.38 g anhydrous MgCl.sub.2 and 0.75 g of the 1:1 molar complex
between TiCl.sub.4 and diethyl malonate are milled together as
described in example 1.
Using 0.5756 g of the thus obtained mixture and polymerizing
propylene under the conditions described in example 1, after 5
hours polymerization, 243 g polypropylene are obtained, which
correspond to a yield of 47,500 g/g Ti. The residue of the extract
ion with boiling n-heptane amounts to 75%. The inherent viscosity
of the crude polymer is=3.64 dl/g.
EXAMPLE 19
4.94 g anhydrous MgCl.sub.2, 4.57 g anhydrous CaSO.sub.4 and 0.92 g
of the complex TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are
milled together, in a nitrogen atmosphere for 40 hours under the
conditions described in example 1.
Using 127.3 mg of the thus prepared mixture (having a titanium
content of 1.25% by weight) and polymerizing propylene under the
conditions described in example 2 after 5 hours reaction, 314 g
polypropylene are obtained which correspond to a yield of 197,000
g/g Ti.
The extraction with boiling n-heptane gave a residue of 80%. The
inherent viscosity of the crude polymer is=3.4 dl/g.
EXAMPLE 20
3.82 g anhydrous MgCl.sub.2, 3.68 g anhydrous CaCO.sub.3 and 0.80 g
of the complex TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are
milled together in a nitrogen atmosphere, for 40 hours under the
conditions described in example 1.
Using 166.9 mg of the thus prepared mixture (having a Ti content of
1.37% by weight), and polymerizing propylene under the conditions
described in example 2, after 5 hours polymerization, 244 g
polypropylene are obtained, which correspond to a yield of 106,500
g/g Ti. The extraction with boiling n-heptane gave a residue of
83.8%.
EXAMPLE 21
2.90 g anhydrous MgCl.sub.2, 4 g anhydrous Na.sub.2 SO.sub.4 and
0.73 g of the complex TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5
are milled together, in a nitrogen atmosphere, for 40 hours under
the conditions described in example 1.
Using 137.2 mg of the thus prepared mixture (having a Ti content of
1.36% by weight) and polymerizing propylene under the conditions
described in example 2, after 5 hours polymerization, 76 g polymer
are obtained which correspond to a yield of 40,800 g/g Ti. The
extraction with boiling n-heptane gave a residue of 78.8%.
EXAMPLE 22
9.52 g anhydrous MgCl.sub.2 and 0.42 g TiCl.sub.3 N(C.sub.2
H.sub.5).sub.2 are milled together in a nitrogen atmosphere for 64
hours, under the conditions described in example 1.
0.366 g of the thus prepared mixture (having a Ti content of
0.89%), are suspended in the solution of 0.82 g Al(C.sub.2
H.sub.5).sub.3 and 0.264 g ethyl benzoate in 50 cm.sup.3 anhydrous
and de-aerated n-heptane.
The thus obtained suspension in injected under pressure of dry
argon, into stainless steel autoclave having a 1 liter capacity
heated to a temperature of 65.degree. C. and containing 310 g
anhydrous propylene. After 5 hours polymerization, 98 g polymer are
obtained which correspond to a yield of 30,000 g/g Ti.
The extraction with boiling n-heptane gave a residue of 70.5%.
EXAMPLE 23
11.777 g anhydrous MgCl.sub.2 and 0.7924 g of the complex
TiCl.sub.4 (CH.sub.3).sub.2 --N--CH.sub.2 --CH.sub.2
--N(CH.sub.3).sub.2 are milled together as described in example
1.
0.2256 g of the thus obtained mixture (having a titanium content of
0.993% by weight) are suspended in the solution of 0.655 g
Al(C.sub.2 H.sub.5).sub.3 and 0.252 g C.sub.6 H.sub.5 COOC.sub.2
H.sub.5 in 50 cm.sup.3 anhydrous n-heptane.
The thus obtained mixture is introduced into a glass flask having a
1 l. capacity, provided with a stirrer and containing 330 g 4
methyl-pentene-1. The whole is stirred and heated to a temperature
of 54.degree. for 8 hours.
The polymerization is then discontinued and 26 g polymer are
separated, which correspond to a yield of 11,520 g/g Ti.
The extraction with boiling n-heptane gave a residue of 80%.
The inherent viscosity of the crude polymer is=4.85 dl/g.
EXAMPLE 24
The complex MgCl.sub.2.pCH.sub.3 OC.sub.6 H.sub.4 --COOC.sub.2
H.sub.5 is reacted at 40.degree. C. for 20 hours with an excess of
Al(C.sub.2 H.sub.5).sub.3 dissolved in n-heptane; the insoluble
product is filtered, suspended again in a solution of Al(C.sub.2
H.sub.5).sub.3 filtered and accurately washed with n-heptane and
dried.
1.0955 of the thus obtained product are suspended in 15 cm.sup.3
toluene containing 0.1113 g of the complex TiCl.sub.4.C.sub.6
H.sub.5 COOC.sub.2 H.sub.5.
This mixture is maintained under agitation for 16 hours at room
temperature; afterward the solvent is removed under vacuum. 0.450 g
of the thus obtained product (containing 1.23% by weight of Ti) are
employed for the preparation of the catalyst and polymerization of
propylene according to example 25 herebelow.
180 g polymer are obtained, which gave a residue to the extraction
with boiling n-heptane=91.5%.
EXAMPLE 25
8.38 g of a mixture of 4.19 g anhydrous MgCl.sub.2 and 4.19 g
anhydrous B.sub.2 O.sub.3 milled in a ball mill and 2.34 g of the
molar complex TiCl.sub.4.ethyl benzoate are milled together in a
nitrogen atmosphere for 110 hours.
0.1164 g of the thus prepared mixture having a Ti-content of 3.08%
by weight are suspended in a solution of 0.82 g Al-triethyl and
0.489 g p.methoxy ethyl benzoate in 50 cm.sup.3 anhydrous and
deareated n-heptane and the thus obtained suspension is injected
under pressure of dry argon into a stainless steel autoclave having
3 l capacity, provided with magnetic stirring heated to 65.degree.
C. and containing 850 g anhydrous propylene and 2 l hydrogen
measured at normal conditions.
After 5 hours of polymerization the unpolymerized propylene is
separated and a white pulverulent product is obtained which after
drying, amounts to 415 g, corresponding to a yield of 115,000 g
polymer per gram of titanium. The extraction with boiling n-heptane
gave a residue 89.5%. The inherent viscosity of the crude polymer
is=2,09 dl/g.
EXAMPLES 26-55
In table 1 are given the results of some examples of polymerization
of propylene conducted under the conditions as described in example
2 but replacing ethylbenzoate complexed with the Al-triethyl by
ethyl-p-methoxy benzoate and replacing ethyl benzoate complexed
with TiCl.sub.4 by the electron-donor compounds indicated in table
1.
The polymerization time was 5 hours.
TABLE 1
__________________________________________________________________________
Residue supported yield in boil- Electron-donor compound used in Ti
% cat. com- p-methoxy g poly- ing n- Example MgCl.sub.2 1:1 molar
complexes with TiCl.sub.4 weight ponent (b) benzoate/Al mer/g
heptane .eta. in No. g g (a) g molar ratio Ti % dl/g
__________________________________________________________________________
26 11.06 0.826 ethyl benzoate 0.995 0.1286 0.39 53100 91.2 4.54 27
10.65 0.81 methyl-otoluate 1.01 0.1210 0.35 114500 89.7 4.22 28
8.54 0.89 t.butyl-p-anisate 1.43 0.1309 0.39 46500 89.5 4.2 29
10.49 0.70 ethyl p-toluate 0.88 0.1204 0.39 94400 90.8 4.68 30 5.96
0.55 coumarin 1.20 0.1190 0.39 117000 88.0 3.62 31 9.83 0.68 ethyl
p-anisate 0.835 0.1214 0.40 127000 89.8 4.54 32 12.60 0.89 ethyl
cinnamate 0.86 0.1554 0.39 113500 88.6 4.10 33 14.93 0.42 ethyl NN
diethylaminoacetate 0.45 0.3443 0.39 58000 90.0 4.2 34 10.92 0.81
ethyl-2-furoate 1.04 0.1417 0.39 102100 89.1 4.06 35 8.89 0.40
.gamma.-butyrrolactone 0.75 0.1330 0.39 50000 89.4 3.72 36 8.49
0.58 t-butyl pivalate 1.06 0.1408 0.39 22100 90.0 4.48 37 9.30 0.66
ethyl pivalate 1.02 0.1431 0.39 118500 89.8 4.32 38 11.45 0.84
.epsilon.-caprolactam 1.07 0.1540 0.39 44800 91.1 4.28 39 12.40
1.03 phthalide 1.10 0.1118 0.39 56900 88.2 3.68 40 9.77 1.03 ethyl
p-anisate (c) 0.81 0.1233 0.39 181000 89.0 4.42 41 9.71 1.19
2-ethoxy-ethyl-p-anisate 1.28 0.1110 0.39 40000 91.2 4.80 42 11.54
0.83 ethyl p-buthoxy benzoate 0.805 0.2281 0.39 99500 89.5 4.52 43
9.98 0.88 ethyl 3.5-dimethylbenzoate 1.08 0.1528 0.39 103000 89.8
4.53 44 10.59 0.79 ethyl p-isopropoxy benzoate 0.88 0.1515 0.39
68500 88.6 4.26 45 9.16 0.73 ethyl p-t-butyl benzoate 0.91 0.1285
0.39 119700 89.0 4.56 46 9.83 1.01 ethyl p-phenylbenzoate 1.09
0.1510 0.39 66000 91.3 4.61 47 11.52 0.9 methyl p-anisate 1.00
0.1690 0.39 59500 90.5 4.32 48 9.2 0.84 ethyl p-acetoxybenzoate
0.93 0.1270 0.39 62700 89.2 4.11 49 8.50 0.74 triphenylphosphine
0.975 0.1750 0.39 51600 89.8 4.53 50 11.48 0.85 N,N diethyl
p-anisamide 0.91 0.1289 0.39 35000 90.3 4.20 51 8.90 0.82
phosphorus oxychloride 1.23 0.1160 0.39 117000 87.5 4.06 52 10.28
0.58 oxathiane 0.89 0.2361 0.39 59500 85.7 3.98 53 11.73 0.87
isoquinoline 0.975 0.1189 0.39 50000 89.4 4.32 54 9.16 0.83
2-ethoxyethyl-pivalate 1.04 0.1012 0.39 46700 89.4 4.78 55 8.82
0.96 diphenylsulphone 1.15 0.1431 0.39 50000 89.3 4.27
__________________________________________________________________________
(a) determined by analysis (b) milled for 16 hours (c) milled for
48 hours; 1:2 molar complex TiCl.sub.4ethyl-p-methoxybenzoate.
EXAMPLE 56
11.8704 g anhydrous MgCl.sub.2 and 0.28 ml TiCl.sub.4 are milled
for 16 hours as described in example 1.
0.2043 g of the so obtained mixture, containing 0.99% titanium, are
suspended in a solution of 0.82 g Al(C.sub.2 H.sub.5).sub.3 and
0.489 g ethyl-p-methoxy benzoate in 50 ml n-heptane, and the
resulting suspension is injected under pressure of argon into a 3
liter autoclave heated to 65.degree. C. and containing 930 g
propylene. After 5 hours polymerization, 200 g polymer are isolated
corresponding to a yield of 99,000 g/g Ti.
The extraction with boiling n-heptane gives a residue of 84.5%.
The inherent viscosity of the crude polymer is 4.14 dl/g.
EXAMPLE 57
4.6515 g anhydrous MgCl.sub.2, 4.6734 g B.sub.2 O.sub.3 dried in
vacuo at 450.degree. C. and 2.5196 g of the complex
TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are milled for 120
hours following the method described in example 1.
0.0508 g of the so obtained mixture (containing 2.99% by weight
titanium) are suspended in a solution previously prepared by
reacting for 10 minutes, in 50 ml n-heptane, 0.665 g Al(C.sub.2
H.sub.5).sub.3 and 0.430 g ethyl alpha-naphthoate, and the
resulting suspension is injected into a 2 liter autoclave heated to
65.degree. C. and containing 2 liter hydrogen and 500 g
propylene.
After 5 hours polymerization, 52 g polymer are obtained
corresponding to a yield of 34,500 g polymer/g titanium employed.
The extraction with boiling n-heptane gives a residue of 85.3%.
The inherent viscosity of the crude polymer is 1.83 dl/g.
EXAMPLE 58
The example 57 is repeated employing in this run 0.0499 g of the
catalyst obtained by co-milling MgCl.sub.2, B.sub.2 O.sub.3 and
TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 and substituting the
ethyl alpha naphthoate by 0.314 g ethyl p-methylbenzoate.
85 g polymer are obtained corresponding to a yield of 57000 g
polymer/g titanium employed.
The residue of the extraction with boiling n-heptane is 85%. The
inherent viscosity of the crude polymer is 2.75 dl/g.
EXAMPLE 59
4.2770 g anhydrous MgCl.sub.2, 4.3553 g B.sub.2 O.sub.3 dried in
vacuo at 450.degree. C. and 2.2718 g of the complex
TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are milled for 110
hours as described in example 1.
0.0673 g of the so obtained product (containing 2.72% by weight
titanium), are suspended in a solution prepared by reacting for 10
minutes, in 50 ml n-heptane, 0.80 g of the compound (C.sub.2
H.sub.5).sub.2 Al-N(C.sub.4 H.sub.9)-Al(C.sub.2 H.sub.5).sub.2 and
0.105 g ethyl p-methoxy benzoate, and the resulting suspension is
injected into a 2 liter autoclave heated to 65.degree. C. and
containing 1.3 liter hydrogen and 500 g propylene.
After 5 hours polymerization 117 g polymer are obtained
corresponding to a yield of 64000 g polymer/g titanium employed.
The residue of the extraction with boiling n-heptane is 88%. The
inherent viscosity of the crude polymer is 2.62 dl/g.
EXAMPLE 60
11.0652 g anhydrous MgCl.sub.2 and 0.826 g of the complex
TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 are milled for 16
hours as described in example 1. 0.3168 g of the so obtained
product (containing 0.995% by weight titanium) are suspended in a
solution prepared by reacting, in 50 ml n-heptane, 0.695 g
Al(i-C.sub.4 H.sub.9).sub.3 and 0.1673 g ethyl benzoate, and the
resulting suspension is injected into a 3 liter autoclave heated to
65.degree. C. and containing 890 g propylene.
After 5 hours polymerization 250 g polymer are obtained
corresponding to a yield of 79,000 g polymer/g titanium employed.
The residue of the extraction with boiling n-heptane is 87.5%. The
inherent viscosity of the crude polymer is 3.94 dl/g.
EXAMPLE 61
9.1156 g of a mixture of equal parts of anhydrous MgCl.sub.2 and
B.sub.2 O.sub.3 dried in vacuo at 450.degree. C., previously milled
for 120 hours in a ball mill, are co-milled with 2.0345 g of the
1:1 molar complex TiCl.sub.4.CH.sub.3 CH.sub.2 COOC.sub.2 H.sub.5
in the same conditions described in example 1, in a nitrogen
atmosphere for 110 hours.
0.054 g of the so obtained product (containing 3% by weight
titanium) are suspended in a solution previously prepared by
reacting for 5 minutes, in 50 ml n-heptane, 0.665 g Al(C.sub.2
H.sub.5).sub.3 and 0.177 g ethyl propionate and the resulting
suspension is injected into a 2 liter autoclave heated to
65.degree. C. and containing 2 liter hydrogen and 500 g
propylene.
After 5 hours the polymerization is stopped and 23 g polymer are
separated corresponding to a yield of 14,200 g polymer/g titanium
employed. The extraction with boiling n-heptane gives a residue of
65%. The inherent viscosity of the crude polymer is 1.74 dl/g.
EXAMPLES 62 to 71
In Table 2 some examples of propylene polymerization are reported
carried out in the same conditions as described in example 2
substituting the electron-donor compounds listed in the table for
the ethyl benzoate.
TABLE 2
__________________________________________________________________________
Residue Electron-donor compound supported Yield in boil- used in
1:1 molar com- Ti % cat. Electron-donor g poly- ing n- Example
MgCl.sub.2 plexes with TiCl.sub.4 weight component compound com-
B/Al mer/g heptane .eta. in No g g (a) (b) g plexed with AlEt.sub.3
molar ratio Ti % dl/g
__________________________________________________________________________
62 7.5 0.65 ethyl cyclohexan- 1.1 0.1 ethylcyclohexan- 0.5 139,000
75 oate oate 63 9.68 1.04 ethyl .beta. naphthoate 1.26 0.1203 ethyl
.beta. naphtho- 0.35 59,300 89.7 4.27 ate 64 10.49 0.70 ethyl
p-methyl- 0.88 0.1686 ethyl p-methyl- 0.33 152,600 85.5 3.62
benzoate benzoate 65 8.75 0.65 sec-butyl p-methoxy 0.89 0.0831
sec-butyl p-me- 0.80 135,300 85. 2.98 benzoate thoxybenzoate 66
11.39 0.82 ethyl p-methoxy ben- 0.87 0.1985 dibutyl 1.3-di- 0.40
177,000 80.1 3.97 zoate oxolane-4.5-di- carboxylate 67 11.54 0.83
ethyl p-n-butoxy- 0.805 0.1766 ethyl p-n-butoxy 0.40 173,300 86.2
4.14 benzoate benzoate 68 9.30 0.66 ethyl pivalate 1.02 0.0938
ethyl pivalate 0.40 320,000 55 69 10.08 1.23 ethyl o-methylben-
1.42 0.1753 ethyl o-methyl 0.30 83,000 87.1 3.78 zoate (c) benzoate
70 8.13 1.11 isobutyl benzoate (c) 1.14 0.1580 isobutylbenzoate
0.30 97,200 85 3.76 71 8.38 0.74 ethyl o-chloroben- 0.95 0.1439
ethyl-o-chloro- 0.30 60,800 89.7 3.97 zoate benzoate
__________________________________________________________________________
(a) Determined by analysis. (b) Milled for 16 hours. (c) Molar
ratio TiCl.sub.4 :electrondonor 1:2.
EXAMPLE 72
9.6 g anhydrous MgCl.sub.2 and 0.405 g TiCl.sub.4 are milled for 16
hours as described in example 1.
0.1307 g of the thus obtained product are suspended in the solution
of 0.665 g Al(C.sub.2 H.sub.5).sub.3 and 0.272 g
ethyl-N,N-diethyl-carbamate in 50 cm.sup.3 n-heptane. The solution
was prepared at room temperature and maintained at this temperature
for 10'.
The thus obtained suspension is injected under pressure of dry
argon into a stainless steel autoclave having a 2 liter capacity,
provided with a stirrer heated to a temperature of 65.degree. C.
and containing 500 g propylene.
After 5 hours polymerization 225 g polymer are obtained, which
correspond to a yield of 173,000 g/g Ti.
The residue to the extraction with boiling n-heptane was 60%.
EXAMPLE 73
A 1:1 by weight mixture of anhydrous MgCl.sub.2, milled for 50
hours in a vibrating mill up to a surface area of 22 m.sup.2 /g,
and B.sub.2 O.sub.3 dried in vacuo at 450.degree. C. was co-milled
in a vibrating mill for 24 hours with the complex TiCl.sub.4
ethylbenzoate used in an amount corresponding to a Ti metal content
in the co-milled product=3% by weight.
The surface area of the co-milled product was 2.8 m.sup.2 /g.
The X rays spectrum of the co-milled product showed a broadening of
the most intense diffraction lines characteristic of the normal
non-activated MgCl.sub.2. 0.5 g of the thus obtained product was
suspended in a solution of 12 g Al(C.sub.2 H.sub.5).sub.3 in 500
cm.sup.3 anhydrous n-heptane containing ethyl-p-methoxy benzoate in
an amount corresponding to a volume ratio with the Al-triethyl of
0.41 to 1.
The suspension is injected into a stainless steel autoclave having
capacity of 30 l provided with a stirrer heated to 65.degree. C.
and containing 10 kg of propylene and 5 l of hydrogen measured at
normal conditions.
After 5 hours polymerization the yield in polypropylene amounted to
192,000 g/g Ti. The extraction with boiling n-heptane gave a
residue of 90%.
EXAMPLE 74
12.9 g of the complex MgCl.sub.2.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5
are reacted at 40.degree. C. for 20 hours with 103 cc of a 1 molar
solution of Al(C.sub.2 H.sub.5).sub.3 in n-heptane. The reaction
mixture is filtered and the solid portion is washed with n-heptane
and dried under vacuum. 5 grams of the thus obtained solid which is
essentially formed of MgCl.sub.2 are added under mechanical
stirring to a 100 cc toluene solution containing 800 mg of the
complex TiCl.sub.4.C.sub.6 H.sub.5 COOC.sub.2 H.sub.5. This mixture
is maintained under agitation for 24 hours at 25.degree. C.;
afterwards the mixture is filtered and the insoluble portion washed
with n-heptane. The titanium content of the solid is 1.24% by
weight.
Into a 3-liter autoclave equipped with magnetic stirrer and
thermoregulated at 60.degree. C. whereinto propylene was made to
flow are introduced in this sequence: 950 cc of n-heptane, a 50 cc
solution in n-heptane of 1.25 cc of Al (isobutyl).sub.3 and of 1.5
cc of methyl paratoluate. After 5 minutes 103 mg of the above
obtained solid complexed product suspended in 20 cc n-heptane are
added thereto.
The autoclave is closed and then there are introduced 0.5 atm
hydrogen and 5 atm propylene. The propylene pressure is kept
constant during the polymerization. After 4 hours the run is
stopped. 30 g of polypropylene are obtained corresponding to a
yield of 23,400 g polypropylene/g Ti, which gives a residue to the
extraction with boiling n-heptane of 90%. The viscosity [.eta.] is
1.8 dl/g.
* * * * *